In conventional "wet" silver halide based color photographic processing systems, an imagewise exposed photographic element is processed in a color developer solution. The developing agent in this developer solution reduces the exposed silver halide of the photographic element to metallic silver, and the resulting oxidized color developing agent reacts with incorporated dye-forming couplers to yield dye images corresponding to the imagewise exposure. Since the metallic silver present desaturates the pure colors of the image dyes, it is desirable to remove the silver from the image area. Silver is conventionally separated from dye image areas by a process of bleaching the silver, often to silver halide, and removing the silver halide by using a fixing bath, or alternatively by incorporating fixing agents into the bleaching bath, to provide a bleach-fix solution.
Bleach-fix solutions commonly contain iron, ammonium, ethylenediaminetetraacetic acid, thiosulfate, and seasoned silver. These components of "wet" silver halide color development processing are the source of much of the pollution from photoprocessing.
Black-and-white images formed in a photographic process are generally produced by developing silver halide in a black-and-white developer to form a silver image. A black-and-white developer, such as hydroquinone, is commonly used to reduce the exposed silver halide to silver metal. The undeveloped silver halide is removed from the print by "fixing" with aqueous sodium thiosulfate. The silver metal remaining in the print represents the image.
In the photographic industry, a photofinisher who wishes to produce both black-and-white and color pictures or prints must have separate processing systems; one for color and one for black-and-white, as the two systems are not compatible. It would, therefore, be advantageous for the photofinisher to have one process capable of producing either black-and-white or color materials.
Conventional Chromogenic Black and White Imaging
Schneider, in U.S. Pat. No. 2,186,736, discloses the use of several color components in one layer for a black-and-white image formation.
Harsh, in U.S. Pat. No. 2,592,514, discloses a color film in which couplers forming more than one color are present in the same layer of the color film.
Scheerer, in U.S. Pat. No. 4,348,474, discloses a system wherein black-and-white images are formed by the use of one emulsion that is treated with three sensitizing dyes.
There have been commercialized products that have formed black-and-white images by the use of pan sensitized emulsions which contain three spectral sensitizing dyes, color dye forming couplers and one emulsion. These pan-sensitive emulsions are sometimes coated in a fast and a slow layer to form images after exposure and development of the couplers. While the above products are somewhat successful, they do not achieve a neutral image. Additionally, the tone reproduction of such materials is severely limited by the contrast range of the emulsion.
Edwards et al., in U.S. application Ser. No. 07/981,566 filed Nov. 25, 1992, published as European Application 0 572 629 disclose chromogenic black and white photographic imaging systems comprising the formation of balanced cyan, magenta, and yellow coupler and emulsion mixes. These systems comprise at least one layer in which silver halide emulsion has been sensitized to blue light or to green light. The grains of silver halide are each sensitized to only a single color, although grains sensitive to different colors may be blended in one layer with the neutrally balanced couplers. Regardless of the color sensitivity of the silver halide layer that contains silver, this layer contains a mixture of cyan, magenta, and yellow dye-forming couplers. In order to obtain a black and white image having a tone scale such as observed by the human eye in a scene, preferred embodiments contain ratios of red sensitive emulsion to green sensitive emulsion to blue sensitive emulsion of about 2:3:1.
Diffusion Transfer Chromogenic Black and White Imaging
King and Stroud, in U.S. Pat. No. 4,563,412, disclose black image dye-providing materials and processes utilizing same, wherein these materials and processes utilize diffusion transfer methods of the instant color photographic variety.
Heat Image Separation Systems
Willis and Texter, in U.S. application Ser. No. 07/804,877, Heat Image Separation Systems, filed Dec. 6, 1991, now U.S. Pat. No. 5,270,145, disclose a process for forming a dye image including the steps of: (a) exposing a photographic element comprising a light sensitive silver halide emulsion layer containing a color coupler compound capable of forming a heat transferable dye upon development; (b) developing the exposed element resulting from step (a) with a color developer solution to form a heat transferable dye image; (c) heating the exposed, developed element resulting from step (b) to thereby transfer the dye image from the emulsion layer to a dye receiving layer which is part of the photographic element or part of a separate dye receiving element brought into contact with the photographic element; and (d) separating the emulsion layer from the dye receiving layer containing the transferred dye image; wherein the color coupler compound is of the following formula (I) EQU COUP-B (I)
wherein COUP represents a coupler moiety capable for forming a heat transferable dye upon reaction of the coupler compound with an oxidized product of the developing solution of step (b); and B is hydrogen or a coupling-off group which is separated from COUP upon reaction of the coupler compound with an oxidized product of the developing solution of step (b). The process combines "wet" development with conventional developing solutions and "dry" separation of the developed image from the emulsion layer by heat transfer.
Bailey et al. in U.S. application Ser. No. 07/804,868, Thermal Solvents for Dye Diffusion in Image Separation Systems, filed Dec. 6, 1991, disclose a photographic chromogenic and substantially dry dye-diffusion-transfer element, wherein said element is activated by heat and comprises contacting dye-receiver and dye-donor layers and further comprises a layer which contains a thermal solvent according to formula (II) ##STR1## wherein Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, and Z.sub.5 are substituents, the Hammet sigma parameters of Z.sub.2, Z.sub.3, and Z.sub.4 sum to at least -0.28 and less than 1.53;
the calculated logP for II is greater than 3 and less than 10. This disclosure is incorporated herein by reference in its entirety for all that it discloses. PA1 Komamura and Nimura, in Kokai Pat. application No. HEI 4[1992]-73751, disclose a method for forming images, characterized by the fact that a photographic photosensitive material having, on a support, a photosensitive layer containing a photosensitive silver halide, dye-forming material, binder, and a thermal solvent, is exposed with an image, and after developing with a liquid, the image-forming material and photosensitive layer surface of the aforementioned photographic photosensitive material is bonded and heated, with all or part of the dye formed as an image on said image-forming material being transferred to the image-forming material. This disclosure is incorporated herein by reference in its entirety for all that it discloses. PA1 L.sup.1 and L.sup.2 are each independently divalent linking groups consisting of groups of 1 to 12 atoms or are independently absent; PA1 m is 1, 2, or 3; PA1 Q comprises a group of 2 to 15 carbon atoms selected from the group consisting of aromatic rings, alkyl rings, or ring-chain combinations, optionally substituted with substituents, Z, consisting of alkyl groups or halogens; PA1 B is a hydrogen bond accepting group with an aqueous pK.sub.a value for proton loss of greater than 6; PA1 n is 1 or 2; PA1 the groups AH and B cannot hydrogen bond to form a ring of either 5 or 6 atoms; PA1 R is an alkyl, aryl and alkylaryl group of from 1 to 18 carbon atoms; PA1 the calculated log of the octanol/water partition coefficient (clogP) is greater than 3 and less than 10. This disclosure is incorporated herein by reference in its entirety for all that it discloses. PA1 exposing a photographic element comprising a support bearing a light sensitive silver halide emulsion layer containing a polymeric color coupler compound capable of forming a heat transferable dye upon development, wherein the polymeric color coupler compound is of the formula (IV) EQU COUP-L-B (IV) PA1 developing said exposed element with a color developer solution to form a heat transferable dye image; PA1 heating said exposed, developed element to thereby transfer the dye image from the emulsion layer to a dye receiving layer, where said receiving layer is part of the photographic element or part of a separate dye receiving element brought into contact with the photographic element; and PA1 separating the emulsion layer from the dye receiving layer containing the transferred dye image. This disclosure is incorporated herein by reference in its entirety for all that it discloses. PA1 Cp is a cyan dye forming radical, magenta dye forming radical, yellow dye forming radical, black dye forming radical, or colorless product forming radical, said Cp being substituted in the coupling position with a divalent linking group, L; PA1 Dye is a dye radical exhibiting selective absorption in the visible spectrum; and PA1 providing an aqueous developable photographic element for forming neutral images comprising balanced cyan, magenta, and yellow heat-diffusible-dye-forming couplers in one or more image forming layers, and further comprising sensitized silver halide, a thermal solvent for nonaqueous, thermal dye-diffusion transfer, and hydrophilic binder, each independently in one or more image forming layers, an integral receiver layer for dye mordanting during nonaqueous, thermal dye-diffusion transfer, and one and only one dimensionally stable support, where said receiver layer is intermediate said support and image forming layers, and wherein said receiver layer and said support may be mechanically separated from said image forming layers by opposing forces; PA1 exposing said element to actinic radiation; PA1 processing said element by contacting said element to an external aqueous bath containing compounds selected from the group consisting essentially of color developer compounds of the primary amine type, compounds which activate the release of incorporated color developers, and compounds which activate development by incorporated developers; PA1 washing said element; PA1 drying said element to remove imbibed water; PA1 heating said element to effect dye-diffusion transfer to an image receiving layer; and PA1 separating said integral receiver layer from said image forming layers. PA1 providing an aqueous developable photographic element for forming neutral images comprising balanced cyan, magenta, and yellow heat-diffusible-dye-forming couplers in one or more image forming layers, and further comprising sensitized silver halide, a thermal solvent for nonaqueous, thermal dye-diffusion transfer, and hydrophilic binder, each of said thermal solvent and hydrophilic binder is independently in one or more image forming layers, and one and only one support; PA1 exposing said element to actinic radiation; PA1 processing said element by contacting said element to an external aqueous bath containing compounds selected from the group consisting essentially of color developer compounds of the primary amine type, compounds which activate the release of incorporated color developers, and compounds which activate development by incorporated developers; PA1 washing said element; PA1 drying said element to remove imbibed water; PA1 contacting said image forming layers of said photographic element with a dry image receiving element comprising an image receiving layer for dye mordanting during nonaqueous, thermal dye-diffusion transfer such that said image forming and image receiving layers are in reactive association with respect to thermally activated dye diffusion transfer, and one and only one dimensionally stable support; PA1 heating said contacting photographic and receiving elements to effect dye-diffusion transfer to said image receiving layer; and PA1 separating said receiving element from said aqueous developable photographic element. PA1 4-amino-N,N-diethylaniline hydrochloride; PA1 4-amino-3-methyl-N,N-diethylaniline hydrochloride; PA1 4-amino-3-methyl-N-ethyl-N-(p-methanesulfonamido-ethyl)aniline sulfate hydrate; PA1 4-amino-3-methyl-N-ethyl-N-(p-hydroxyethyl) aniline sulfate; PA1 4-amino-3-(p-methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride; PA1 4-amino-3-methyl-N-ethyl-N-(p-methanesulfonamido-ethyl)aniline sesquisulfate monohydrate; and PA1 4-amino-3-methyl-N-ethyl-N-(2-methoxyethyl)aniline di-p-toluenesulfonic acid.
Bailey et al. in U.S. application Ser. No. 08/073,821, Hydrogen Bond Donating/Accepting Thermal Solvents for Image Separation Systems, filed Jun. 8, 1993, disclose an aqueous-developable chromogenic photographic heat-transferable non-aqueous dye-diffusion-transfer photographic element, wherein this element comprises radiation sensitive silver halide, a dye-providing compound that forms or releases a heat-transferable image dye upon reaction of said compound with the oxidation product of a primary amine developing agent, a hydrophilic binder, and a thermal solvent for facilitating non-aqueous diffusion transfer according to formula (III) ##STR2## wherein AH is a hydrogen bond donating group with an aqueous pK.sub.a value for proton loss of greater than 6;
Texter et al. in U.S. application Ser. No. 07/927,691, Polymeric Couplers for Heat Image Separation Systems, filed Aug. 10, 1992, disclose a process for forming a dye image including the steps of:
wherein COUP represents a coupler moiety capable of forming a heat transferable dye upon reaction of the moiety with an oxidation product of a color developer; L is a divalent linking group which is separated from COUP upon reaction of the coupler moiety with said oxidation product of a color developer; and B represents the polymeric backbone;
Texter et al. in U.S. application Ser. No. 07/993,580, Dye-Releasing Couplers for Heat Image Separation, filed Dec. 21, 1992, disclose an aqueous-developable photographic color diffusion transfer element comprising a single dimensionally stable support and one or more layers comprising radiation sensitive silver halide, thermal solvent for facilitating the thermal diffusion of dyes through a hydrophilic binder, a dye-releasing coupler, and hydrophilic binder, wherein said dye is heat diffusible in said binder and thermal solvent, and wherein said dye-releasing coupler is of the formula (V) EQU Cp-L-Dye (V)
where
where said -L-Dye group couples off upon reaction of said coupler radical with the oxidation product of a primary amine developing agent. This disclosure is incorporated herein by reference in its entirety for all that it discloses.